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United States Patent FLUORESCENT AGENT William W. Williams, NeW York, N. Y., and William H.

' detergents, the fluorescent material which is employed Libby, St. Paul, Minn., assignors to General Aniline'&

Film Corporation, New York, N. Y., a corporation of Delaware 1 No Drawin Application March 30, 1950 Serial No. 575,000

5 cl ims. (Cl. 260-2471) The invention here presented is anew whitener in the form of a dye type of substance which is fluorescent under ultra violet to yield a brilliant bluish white fluorescence, which agent is found in the triaz inostilbene series. a

It is well known that cellulosic materials such as paper, cotton textiles and the like have a slight yellowish hue which, particularly in the case of textile materials, is apt to become more pronounced when the material is subjected to repeated launderings and use. Accordingly, it has long been the practice to treat many white cotton textiles, when they are washed, with a bluing substance, such as ultramarine. It has been'found that the slight blue coloration thus imparted to the material compensates for the yellowish tint or similar off-white shade of the material so that it appears whiter; such bluing operations, however, result in the absorption of a measurable portion of the total visible light falling upon the treated material and, accordingly, the treated material has a silghtly dull appearance. 7 I It has recently been proposed to treat paper or cotton textiles and similar cellulosic materials with agents which, while themselves colorless, fluoresce in the blue range of the spectrum so that in daylight or other light, which includes ultra violet radiation, the fluorescence of the treating agent compensates for the slight yellowish tint or similar oil-white shade, the blue'being complementary to yellow. Such fluorescent agents only absorb, a negligible portion of the visible light falling on the material and, accordingly, as a result-of the fluorescence the treated material is much brighter as well as whiter in appearance.

While a wide variety of fluorescent agents have been suggested for treatment of fibrous materials, it has been found that for the treatment of cellulosic materials, either paper or textiles, the use of fluorescent agents which are substantive to cellulose is preferable since by'the use of substantive fluorescent agents a whitening or brightening the material so that after drying the material appears much whiter and brighter than untreated materials.

These fluorescent brightening agents are also useful in treating textile materials which are to be, or have been dyed or printed withdischarge paste. The whites of the materials so printed with pastes containing brightening agents are much whiter than is otherwise the case.

While numerous fluorescent bleaching or brightening agents have heretofore been suggested, including diaminostilbene sulfonic and carhoxylic acids and certain acylated derivatives thereof, only a few of them have been satis factory, particularly for use by incorporation in soap or other detergents. Inorder to be satisfactory for use as a brightening agentto be incorporated with soap or similar ground of photographic prints and diazotype prints can be i coating emulsions.

. charge pastes, the whites obtained upon discharge are decidedly whiter than those discharges made in the abfabrics.

should be itself colorless, or nearly so, and must not stain yellow tints to thetreated fabric. It must also have a proper degree of substantivity towards the materials as too small adegree of substantivity renders it valueless as if would be'removed in any rinse waters, and too high a degree of substantivity results in a gradual build-up of fluorescent agent on material during repeated launderings resulting in off-color shades. The fluorescent agent must be stable to light and notdiscolor on exposure. ,It must be stable to hyp'o-chlorite treatment,andnotj discolor under suchtreatment, and in addition, it must fluoresce overa fairly wide pH differential, including both alkali and acid. W The present invention presents a series of compounds which have some of the characteristics of dyestuffs or pigments, which in addition show a strong bluish white fiuoresence of out-standing brilliance, which compounds in addition are readily incorporated into a wide range. of fabrics, fibers, felted materials and paper, to yield an outstanding whiteness in the material to which they are applied. .This material is a triazinostilbene compound containing a semicarbazide group with an associated alkyl amino group. Broadly the compound has the following molecular structure:

X 2 K N C-NH- CH: C=N S O 3N8.

111a 1 TH C O NH: 2

Where X is selected from the group consisting of morpholino, dimethylamino, diethylamino or di-(hydroxyethynamino substituents. A w a I This compound, and a considerable group of analogous compounds, are readily preparedby condensingl molecular proportion of 4,4-diamino-2,2'-stilbene-disulfonic acid with 2 molecular proportions of cyanuric chloride. The primary condensation product can be :further condensed with 2 molecular proportions of semi-carbazide hydrochloride and finally with 2 molecular proportions of morpholine, dimethylamine, diethylamine or diethanolamine.

These materials are particularly useful for application to paper or fabrics or other sheet or wrapping material to 5 improve the whiteness thereof. They are useful when applied to fabrics by methods well known in the art since the whiteness is remarkably improved. The white backimproved by incorporating some of the material into the By addition of the substances to dissence of said materials. If small quantities of these materials are used in soaps or other detergents, fabrics which are washed using these formulations will be much whiter in the case of whites and much brighter 'in the case'of colors th an fabrics which are washed with ordinary soaps or detergents. These materials may be usedto bleach In such cases, the amount of bleach necessary is materially reduced and one or more steps in the normal bleaching operation may be eliminated. 7

Thus the product of the invention outstandingly increases the apparent whiteness of a wide range of surfacing materials by the incorporationathereinto of a dye 3 type substance of the triazinostilbene series containing a semicarbazide group and an alkyl amine substituent.

cooled and the product is separated in the usual manner. It corresponds to the formula:

other' objects' and details of theinvention will be apparent from thefollowing description.

" The following examples show the preferred method of practising the invention but various modifications will be obvious to those skilled in the art.

Example I Thirty-seven parts of'cyanuric' chloride are dissolved in 120 parts of acetone and poured into a mixture of ice and water; During the suspension in ice water, the temperatureof the aqueous suspension should not rise above 5 C. Thirty-seven parts of 4,4-diaminostilbene-2,2-disulfonic acid are dissolved in 150 parts of water with the additionof enough sodium carbonate to give a neutral The materialwhich is obtained is slightly tan in color and moderately soluble in water but very slightly soluble in acetone, alcohol, ether, etc.

Example 11 The procedure of Example I was repeated up to and including the end of the secondary condensation whereupon, instead of adding 56 parts of morpholine, 142 parts of a 33% aqueous solution of dimethylamine were added and the pH increased to 7.5 to 7.8 with sodium carbonate solution. Then the mixture was heated slowly to 65 C. and maintained at that temperature for 8 hours, as before. Upon cooling and separating the product a material was obtained corresponding to the formula:

The material which is obtained is slightly tan in color and moderately soluble in water but very slightly soluble in acetone, alcohol, ether and the like.

Example Ill The procedure of Example I was repeated up to and including the secondary condensation; then instead of adding. 56 parts of morpholine, 73 parts of diethylamine were addedand the material neutralized and heated as be fore to yield a product corresponding to the formula:

N-omon,

partstof semicarba'zide hydrochloride is added and immediately, afterward a solution of 160 parts of anhydrous sodium acetate in 400 parts of water is added. The mixture is allowed to warm to room temperature and may be heated to 35-40 C. ifnecessary to complete the condensation. When this secondary, condensation is complete, 56 parts of morpholineare added and the pH is increased to 7.5-8 with sodium carbonatesolution. Then the mixture is heated slowly to f C. and maintained SOrN SOxNa NCH:CH;

The material which is obtained is slightly tan in color and moderately soluble in water but very slightly soluble in acetone, alcohol, ether and the like.

Example IV The procedure of Example I was repeated, as before,

up to and including the secondary condensation; then instead of the 56 parts of morpholine, there were added at that temperature for 8 hours. The mixture is then 68 parts of diethanolamine, after which, the processing shown in Example I was repeated to yield a compound having the formula:

C-N some N=C soma N-CHiCHflOH N -ornomon mcrnon The material which is obtained is slightly tan in color a l embodiments of 'theprocess of the invention it is possible and moderately soluble in water but very slightly soluble to provide still other embodiments without departing from in acetone, alcohol, ether and the like. r vthe inventive concept'herein disclosed and it is there- It may be noted that in all of these 4 examples, the X foreJdesired that only' such limitations be imposed upon substituent, as shown in the first structural formula, may". theappended claims as are stated therein or required by consist of a morpholino, dimethylamino, diethylamino, or the prior art. 1

a dihydroxy ethylamino substituent. The invention claimed is:

When this material is incorporated into discharge pastes 1. A whitener having the composition:

and applied to fabrics, the whites thus obtained were re- 25 X markably whiter than those obtained using ordinary dis- I N charge pastes. When this material is applied to fibers of cellulose, wool or nylon, by methods well known in the N art, the white appearance of the fabric is thereby much C=N so improved. 30 NH If small amounts of this substance are added to soap or NHOONH: 2

detergent and the resulting mixture is used to wash fabrics of cellulose, wool or nylon, the white materials thus washed are extraordinarily whiter in appearance and colored materials are brighter than similar materials 35 ethyl)-arnino.

which are washed using ordinary soaps or detergents. 2. whitener having the composition:

where X is selected from the group consisting of morpholinyl, dimethylamino, diethylamino and di-(hydroxy- 1 TH N'HC ONH: in in;

6: N-JJ CHzC 1 C-N SOrNa N=C CHZCHQ \l l o 7 N so.Na 0 cflscg oflacfia The product and process of the invention thus provide 3. A whitener having the composition:

0 O-NHB I IH NHC ONHi I IH VNH N %CNHQCH=OH- 'NHC\ /N o-N SOzNa N=C H3C-IT SoaHa H;C11I (3E3 H3 material and procedures for outstandingly increasing the 4. A whitener having the composition:

H NHC ONH, r m NH Q K 1 CNH OH=GH@NHO\ /N C-N SOSNa N=C V SOaNa N-C'HzCHa N-CHzCH;

HzCH; aC a 7 smA Wvhitenem h -cmcmon HaCHlOH SOIN aving the composition 1 NHCONH,

References Cited in the file of this patent UNITED STATES PATENTS Hein et a1. Sept. 7, 1954 

1. A WHITENER HAVING THE COMPOSITION: 